JP3770608B2 - Halogen gas absorber, halogen gas removal method and halogen gas processing apparatus - Google Patents

Halogen gas absorber, halogen gas removal method and halogen gas processing apparatus Download PDF

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JP3770608B2
JP3770608B2 JP2003319963A JP2003319963A JP3770608B2 JP 3770608 B2 JP3770608 B2 JP 3770608B2 JP 2003319963 A JP2003319963 A JP 2003319963A JP 2003319963 A JP2003319963 A JP 2003319963A JP 3770608 B2 JP3770608 B2 JP 3770608B2
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halogen gas
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雅礼 加藤
和明 中川
佐和子 吉川
健司 越崎
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Description

本発明は、ハロゲンガスを含有する気体中からハロゲンガスを除去するハロゲンガス吸収材、このハロゲンガス吸収材を用いたハロゲンガスの吸収方法、ハロゲンガスを吸収したハロゲンガス吸収材からハロゲンガスを回収するハロゲンガス回収方法及び、ハロゲンガス処理装置に関する。   The present invention relates to a halogen gas absorbing material for removing halogen gas from a gas containing halogen gas, a halogen gas absorbing method using the halogen gas absorbing material, and recovering the halogen gas from the halogen gas absorbing material that has absorbed the halogen gas. The present invention relates to a halogen gas recovery method and a halogen gas processing apparatus.

現在、半導体製造プロセスのドライエッチング工程などでは、除去する膜の性質に応じて各種のドライエッチングガスが使用されており、例えばフッ化水素酸ガスや、三フッ化塩素などのハロゲンガスをエッチングガスとして不活性ガスと共に供給してドライエッチングが行われている。   Currently, various dry etching gases are used in the dry etching process of the semiconductor manufacturing process depending on the properties of the film to be removed. For example, hydrofluoric acid gas or halogen gas such as chlorine trifluoride is used as an etching gas. As described above, dry etching is performed by supplying together with an inert gas.

そして、これらのハロゲンガスは危険性や毒性が高いために、不活性ガス中から除去した後に排出する必要がある。   And since these halogen gases are highly dangerous and toxic, they must be discharged after being removed from the inert gas.

一方、ハロゲンガスの除去方法としては、湿式法と乾式法とが知られている。   On the other hand, wet methods and dry methods are known as methods for removing halogen gas.

湿式法は、アルカリ水溶液をハロゲンガスの吸収液として使用するもの方法であるが、この方法は微量のハロゲンガスに対して除去効率が低いという問題がある。   The wet method is a method in which an alkaline aqueous solution is used as a halogen gas absorbing solution. However, this method has a problem that the removal efficiency is low for a very small amount of halogen gas.

乾式法としては、二種類のアルカリ成分を含有する粒子をハロゲンガス吸収材として用いる方法があり、この方法では、ガスの回収も比較的簡便な方法で行える。例えば、ソーダライム（ＮａＯＨ、Ｃａ（ＯＨ）2、Ｈ2Ｏ）を吸収材として用いて塩化水素ガスを除去する場合、以下の化学式（１）乃至（３）に示す反応が順次生じて、塩化水素ガスを除去する。 As a dry method, there is a method in which particles containing two kinds of alkali components are used as a halogen gas absorber, and in this method, gas can be recovered by a relatively simple method. For example, when hydrogen chloride gas is removed using soda lime (NaOH, Ca (OH) 2 , H 2 O) as an absorbent, reactions shown in the following chemical formulas (1) to (3) occur sequentially, Remove hydrogen gas.

ＨＣｌ＋Ｈ2Ｏ → Ｈ3ＣｌＯ・・・(1)
Ｈ3ＣｌＯ＋ＮａＯＨ → ＮａＣｌ＋２Ｈ2Ｏ・・・(2)
ＮａＣｌ＋1/2Ｃａ（ＯＨ）2→ 1/2ＣａＣｌ2＋ＮａＯＨ・・・(3)
しかしながら、式（１）で示すように、ソーダライムでハロゲンガスを除去するためには水分が必要であり、ドライエッチングガスのように、乾燥したガス中でソーダライムを使用すると、水分が蒸発してしまうため、ドライエッチングガスに使用されるハロゲンガスを除去することは困難である。 HCl + H 2 O → H 3 ClO (1)
H 3 ClO + NaOH → NaCl + 2H 2 O (2)
NaCl + 1 / 2Ca (OH) 2 → 1 / 2CaCl 2 + NaOH (3)
However, as shown by the formula (1), moisture is required to remove halogen gas with soda lime, and when soda lime is used in a dry gas such as dry etching gas, the moisture evaporates. Therefore, it is difficult to remove the halogen gas used for the dry etching gas.

また、特開平９−９９２１６号公報には、ＮａＯＨの代わりに水酸化ストロンチウムを使用することで水分量の低減によるハロゲンガス吸収能の低下を防止したハロゲンガス吸収材が開示されているが、この技術にしても反応に水分は必要であり、乾燥雰囲気下にけるハロゲンガスの吸収には限界があり、頻繁に吸収材を交換しなければならない。
特開平９−９９２１６号公報（第３頁） Japanese Patent Laid-Open No. 9-99216 discloses a halogen gas absorbent that uses a strontium hydroxide instead of NaOH to prevent a decrease in halogen gas absorption capacity due to a reduction in water content. Even with technology, moisture is required for the reaction, and there is a limit to the absorption of halogen gas in a dry atmosphere, and the absorbent material must be frequently replaced.
JP-A-9-99216 (page 3)

上述したように、湿式法によるハロゲンガス除去はハロゲンガスの回収が困難であり、アルカリ成分を含有する粒子を用いた乾式法においては、乾燥したガス中からハロゲンガスを除去することに適していなかった。   As described above, the halogen gas removal by the wet method is difficult to recover the halogen gas, and the dry method using particles containing alkali components is not suitable for removing the halogen gas from the dried gas. It was.

本発明のハロゲンガス吸収材は、ハロゲンガスを含有する気体中からハロゲンガスを吸収するハロゲンガス吸収材であって、平均粒径５０μｍ以上、３ｍｍ以下のリチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有することを特徴とする。
前記粒子は、Ｌｉ4ＳｉＯ4またはＬｉ2ＺｒＯ3であることが好ましい。 The halogen gas absorber of the present invention is a halogen gas absorber that absorbs a halogen gas from a gas containing a halogen gas, and is selected from lithium silicate, lithium zirconate, and lithium titanate having an average particle size of 50 μm or more and 3 mm or less. It is characterized by containing at least one kind of particles .
The particles are preferably Li 4 SiO 4 or Li 2 ZrO 3 .

また、本発明のハロゲンガス吸収材は、ハロゲンガスを含有する気体中からハロゲンガスを吸収するハロゲンガス吸収材であって、リチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有する気孔率３０％以上、７０％以下の多孔質体からなる平均粒径５０μｍ以上、３０ｍｍ以下の粒子であることを特徴とする。 The halogen gas absorber of the present invention is a halogen gas absorber that absorbs a halogen gas from a gas containing a halogen gas, and particles comprising at least one selected from lithium silicate, lithium zirconate, and lithium titanate. It is characterized by being particles having an average particle diameter of 50 μm or more and 30 mm or less made of a porous material having a porosity of 30% or more and 70% or less.

本発明のハロゲンガスの除去方法は、ハロゲンガスを含有する気体を、平均粒径５０μｍ以上、３ｍｍ以下のリチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子に接触させることを特徴とする。 The halogen gas removal method of the present invention is characterized in that a gas containing a halogen gas is brought into contact with particles composed of at least one selected from lithium silicate, lithium zirconate, and lithium titanate having an average particle size of 50 μm to 3 mm. And

また、本発明のハロゲンガスの除去方法は、ハロゲンガスを含有する気体を、リチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有する気孔率３０％以上、７０％以下の多孔質体からなる平均粒径５０μｍ以上、３０ｍｍ以下の粒子に接触させることを特徴とする。 In the halogen gas removal method of the present invention, the gas containing the halogen gas has a porosity of 30% or more and 70% or less containing particles composed of at least one selected from lithium silicate, lithium zirconate, and lithium titanate . It is characterized by contacting with particles having an average particle diameter of 50 μm or more and 30 mm or less made of a porous material.

本発明のハロゲンガス処理装置は、ハロゲンガスを含有する気体を導入する導入口、及び排出口を有する容器と、前記容器内に充填された、平均粒径５０μｍ以上、３ｍｍ以下のリチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子とを具備することを特徴とする。 The halogen gas treatment apparatus of the present invention includes a container having an inlet for introducing a gas containing a halogen gas and a discharge port, a lithium silicate having an average particle size of 50 μm or more and 3 mm or less filled in the container, lithium silicate, And particles comprising at least one selected from zirconate and lithium titanate .

また、本発明のハロゲンガス処理装置は、ハロゲンガスを含有する気体を導入する導入口、及び排出口を有する容器と、前記容器内に充填された、リチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有する気孔率３０％以上、７０％以下の多孔質体からなる平均粒径５０μｍ以上、３０ｍｍ以下の粒子とを具備することを特徴とする。 Further, the halogen gas processing apparatus of the present invention is selected from a container having an inlet for introducing a gas containing a halogen gas and an outlet, and lithium silicate, lithium zirconate, and lithium titanate filled in the container. And particles having an average particle diameter of 50 μm or more and 30 mm or less made of a porous material having a porosity of 30% or more and 70% or less containing particles composed of at least one kind .

本発明によれば、乾燥したガス中からハロゲンガスを効率よく吸収することが可能になる。 According to the present invention, it is possible to efficiently absorb halogen gas from dried gas .

（第１の実施形態）
第１の実施形態に用いられるハロゲンガス吸収材は、リチウム化複合酸化物を含有している。 (First embodiment)
The halogen gas absorber used in the first embodiment contains a lithiated composite oxide.

リチウム化複合酸化物とは、具体的には、リチウムシリケート、リチウムジルコネート、リチウムフェライト、リチウムニッケレート、リチウムチタネート、リチウムアルミネートなどが挙げられ、これらの成分を複数含有していても構わない。   Specific examples of the lithiated composite oxide include lithium silicate, lithium zirconate, lithium ferrite, lithium nickelate, lithium titanate, lithium aluminate, and the like, and a plurality of these components may be contained. .

このようなリチウム複合酸化物の粉末は、酸化ケイ素は、酸化ジルコニウム、酸化鉄、酸化ニッケル、酸化チタン、酸化アルミニウムなどの金属酸化物粉末と、炭酸リチウム粉末とを反応させることで製造することができる。これらの原料紛は、例えば平均粒径０．１μｍ〜２０μｍのものを使用すればよい。具体的に、リチウムシリケート、リチウムジルコネートの生成反応を以下の式（４）、（５）に示す。   Such lithium composite oxide powder can be produced by reacting silicon oxide with lithium carbonate powder and metal oxide powder such as zirconium oxide, iron oxide, nickel oxide, titanium oxide, and aluminum oxide. it can. As these raw material powders, for example, those having an average particle diameter of 0.1 μm to 20 μm may be used. Specifically, the formation reaction of lithium silicate and lithium zirconate is shown in the following formulas (4) and (5).

SiO2＋2Li2CO3→Li4SiO4＋2CO2・・・(4)
ZrO2＋Li2C O3→Li2ZrO3＋CO2・・・(5)
リチウムシリケート、リチウムジルコネート、リチウムフェライト、リチウムニッケレート、リチウムチタネート、リチウムアルミネートの反応温度はそれぞれ、400℃以上、500℃以上、300℃以上、400℃以上、400℃以上、500℃以上である。なお、これらの反応は可逆的なものであって、前述した温度よりも低温になるとリチウム化複合酸化物は金属酸化物に戻ってしまう。そのため、製造されたリチウム化複合酸化物は、密閉容器など二酸化炭素を除去した環境で保存することが望ましい。 SiO 2 + 2Li 2 CO 3 → Li 4 SiO 4 + 2CO 2 (4)
ZrO 2 + Li 2 CO 3 → Li 2 ZrO 3 + CO 2 (5)
The reaction temperature of lithium silicate, lithium zirconate, lithium ferrite, lithium nickelate, lithium titanate, and lithium aluminate is 400 ° C or higher, 500 ° C or higher, 300 ° C or higher, 400 ° C or higher, 400 ° C or higher, 500 ° C or higher, respectively. is there. These reactions are reversible, and the lithiated composite oxide returns to the metal oxide when the temperature is lower than the above-described temperature. Therefore, it is desirable to store the manufactured lithiated composite oxide in an environment from which carbon dioxide has been removed, such as a sealed container.

次に、ハロゲンガスの吸収反応について説明する。   Next, the absorption reaction of the halogen gas will be described.

ハロゲンガスとして塩化水素ガスを使用した場合の、これらのリチウム複合酸化物の吸収反応を以下の化学式（６）〜（１２）に示す。   The absorption reactions of these lithium composite oxides when hydrogen chloride gas is used as the halogen gas are shown in the following chemical formulas (6) to (12).

Li4SiO4(s)＋4HCl→4LiCl(s)＋SiO2(s)＋2H2O・・・(6)
Li2SiO3(s)＋2HCl→2LiＣｌ(s)＋SiO2(s)＋H2O・・・(7)
Li2ZrO3(s)＋2HCl→2LiＣｌ(s)＋ZrO2(s)＋H2O・・・(8)
2LiFeO2(s)＋2HCl→2LiＣｌ(s)＋Fe2O3(s)＋H2O・・・(9)
2LiNiO2(s)＋2HCl→2LiＣｌ(s)＋Ni2O3(s)＋H2O・・・(10)
Li 2TiO3(s)＋2HCl→2LiＣｌ(s)＋TiO2(s)＋H2O・・・(11)
2LiAlO2(s)＋2HCl→2LiＣｌ(s)＋Al2O3(s)＋H2O・・・(12)
なお、リチウムシリケートは、式（６）、（７）で示すように２種類あるが、式（６）で示したリチウムシリケート（Ｌｉ4ＳｉＯ4）は、式（７）〜（１２）で示すリチウム化複合酸化物に対して理論的に２倍（モル比）のハロゲンガスを回収することが可能である。 Li 4 SiO 4 (s) + 4HCl → 4LiCl (s) + SiO 2 (s) + 2H 2 O (6)
Li 2 SiO 3 (s) + 2HCl → 2LiCl (s) + SiO 2 (s) + H 2 O (7)
Li 2 ZrO 3 (s) + 2HCl → 2LiCl (s) + ZrO 2 (s) + H 2 O (8)
2LiFeO 2 (s) + 2HCl → 2LiCl (s) + Fe 2 O 3 (s) + H 2 O (9)
2LiNiO 2 (s) + 2HCl → 2LiCl (s) + Ni 2 O 3 (s) + H 2 O (10)
Li 2 TiO 3 (s) + 2HCl → 2LiCl (s) + TiO 2 (s) + H 2 O (11)
2LiAlO 2 (s) + 2HCl → 2LiCl (s) + Al 2 O 3 (s) + H 2 O (12)
There are two types of lithium silicate as shown in formulas (6) and (7), but the lithium silicate (Li 4 SiO 4 ) shown in formula (6) is shown in formulas (7) to (12). It is possible to recover a halogen gas that is theoretically twice (molar ratio) to the lithiated composite oxide.

本発明のハロゲンガス吸収材は、塩化水素ガスに限らず、フッ素ガス、塩素ガス、塩化水素ガス、フッ化塩素ガス、臭素ガス、臭化水素ガス、ヨウ素ガス、ヨウ化水素ガスなど、各種ハロゲンガスの吸収に使用することができる。   The halogen gas absorbent of the present invention is not limited to hydrogen chloride gas, but various halogens such as fluorine gas, chlorine gas, hydrogen chloride gas, chlorine fluoride gas, bromine gas, hydrogen bromide gas, iodine gas, and hydrogen iodide gas. Can be used for gas absorption.

Li4SiO4(s)＋ClF3 →3LiF(s)＋LiClO2(s)＋SiO2 ・・・(13)
Li4SiO4(s)＋4HF→4LiF(s)＋SiO2(s)＋2H2O ・・・(14)
第１の実施形態においては、このリチウム化複合酸化物は平均粒径５０μｍ以上、３ｍｍ以下の顆粒として使用することを特徴としている。 Li 4 SiO 4 (s) + ClF 3 → 3LiF (s) + LiClO 2 (s) + SiO 2 (13)
Li 4 SiO 4 (s) + 4HF → 4LiF (s) + SiO 2 (s) + 2H 2 O (14)
In the first embodiment, the lithiated composite oxide is used as granules having an average particle size of 50 μm or more and 3 mm or less.

平均粒径が５０μｍよりも小さい粉末を使用すると、粒子同士が密に詰まり粒子間の隙間が小さくなるため、粉末中を流れる被処理ガス（前述したようなハロゲンガスを含有した気体）の流量を確保することが困難になり、ハロゲンガスを効率よく吸収することができなくなるおそれがある。一方、平均粒径が３ｍｍを超える粒子を使用すると、リチウム化複合酸化物とハロゲンガスとの接触確率（接触面積／体積）が小さくなるため、ハロゲンガスの吸収効率が低下する。   When a powder having an average particle size smaller than 50 μm is used, the particles are closely packed and the gap between the particles is reduced, so that the flow rate of the gas to be processed (the gas containing the halogen gas as described above) flowing in the powder is reduced. It may be difficult to ensure, and the halogen gas may not be absorbed efficiently. On the other hand, when particles having an average particle size exceeding 3 mm are used, the probability of contact between the lithiated composite oxide and the halogen gas (contact area / volume) decreases, so the halogen gas absorption efficiency decreases.

従来のソーダライムのようなハロゲンガス吸収材は、式（１）で示したように反応するためには、水分を必須成分としているため、乾燥ガス中で使用する際には粒径５ｍｍ程度の粗大粒子を用いるなどして保湿性を高める必要があった。これに対してリチウム化複合酸化物は、式（６）〜（１４）で示されるようにハロゲンガスとの反応に水分を必要としないため、平均粒径３ｍｍ以下とすることが可能になり、前述したようにハロゲンガスとの接触確率を高め、ハロゲンガスを効率よく吸収することが可能になる。   Conventional halogen gas absorbers such as soda lime have moisture as an essential component for the reaction as shown in the formula (1). Therefore, when used in a dry gas, the particle size is about 5 mm. It was necessary to improve the moisture retention by using coarse particles. On the other hand, since the lithiated composite oxide does not require moisture for the reaction with the halogen gas as shown by the formulas (6) to (14), the average particle size can be 3 mm or less. As described above, the contact probability with the halogen gas is increased, and the halogen gas can be efficiently absorbed.

リチウム化複合酸化物粉末を平均粒径５０μｍ〜３ｍｍ程度の顆粒状にする方法としては、転動法やスプレードライ法などが挙げられる。   Examples of the method of making the lithiated composite oxide powder into granules having an average particle size of about 50 μm to 3 mm include a rolling method and a spray drying method.

転動法は平均粒径０．０５〜３ｍｍ程度の比較的粒径の大きな顆粒を製造するのに適しており、例えば、０．１〜２０μｍ程度のリチウム化複合酸化物粉末と、バインダ樹脂粉末とを重量比で１：０．００５〜０．１の比率で混合した混合物を、傾斜回転皿の回転速度を５０ｒｐｍ〜５００ｒｐｍ程度で、１〜６０ｍｉｎ程度の処理を行うことで得ることができる。バインダ樹脂としては、ＰＶＡ（ポリビニルアルコール）、ＰＶＢ（ポリビニルブチラール）、ワックス、パラフィン、ＣＭＣ（カルボキシルメチルセルロース）等を使用することができる。ＰＶＡ、ＣＭＣのような特性の樹脂を用いると比較的粒径が大きくなり、ＰＶＢ、ワックスのような特性のバインダ樹脂を用いると比較的粒径の小さな顆粒が得られる。また、処理時間を長くする、あるいは回転速度を小さくするほど、平均粒径が大きくなる。   The rolling method is suitable for producing granules having an average particle size of about 0.05 to 3 mm and a relatively large particle size. For example, a lithiated composite oxide powder of about 0.1 to 20 μm and a binder resin powder Can be obtained by performing a treatment for about 1 to 60 minutes at a rotational speed of the inclined rotating pan of about 50 rpm to about 500 rpm. As the binder resin, PVA (polyvinyl alcohol), PVB (polyvinyl butyral), wax, paraffin, CMC (carboxyl methyl cellulose) and the like can be used. When a resin having characteristics such as PVA and CMC is used, a relatively large particle diameter is obtained. When a binder resin having characteristics such as PVB and wax is used, granules having a relatively small particle diameter are obtained. Further, the longer the processing time or the lower the rotation speed, the larger the average particle size.

スプレードライ法は１０μｍ〜５００μｍ程度の比較的粒径の小さな顆粒を製造するのに適しており、例えば、０．１〜２０μｍ程度のリチウム化複合酸化物粉末に、水とバインダ樹脂とを添加してスラリーを調整し、このスラリーを熱風が循環している炉内に噴霧すれば良い。調整するスラリーの粘度を調整することで得られる顆粒のサイズを調整でき、スラリーの粘度が高くなるにしたがって、その粒径は大きくなる。具体的にはスラリーの粘度が１０ｍＰａ・ｓ〜５００ｍＰａ・ｓ程度となるように、バインダ樹脂や水の添加量を調整すれば良い。
（第２の実施形態）
第２の実施形態に用いられるハロゲンガス吸収材は、組成、製造工程における原料や反応式、被処理ガス中に含有されるハロゲンガスの種類、ハロゲンガスとの反応式、ハロゲンガスを吸収した吸収材からのハロゲンガスの回収・抽出方法等については、第１の実施形態と同様である。 The spray drying method is suitable for producing granules having a relatively small particle size of about 10 μm to 500 μm. For example, water and a binder resin are added to a lithiated composite oxide powder of about 0.1 to 20 μm. The slurry may be adjusted and sprayed into the furnace in which the hot air is circulating. The size of the granules obtained can be adjusted by adjusting the viscosity of the slurry to be adjusted, and the particle diameter increases as the viscosity of the slurry increases. Specifically, the amount of binder resin or water added may be adjusted so that the viscosity of the slurry is about 10 mPa · s to 500 mPa · s.
(Second Embodiment)
The halogen gas absorbing material used in the second embodiment includes the composition, the raw material and reaction formula in the manufacturing process, the type of halogen gas contained in the gas to be treated, the reaction formula with the halogen gas, and the absorption absorbed by the halogen gas. The method for recovering and extracting the halogen gas from the material is the same as in the first embodiment.

第２の実施形態においては、ハロゲンガス吸収材が、気孔率３０％〜７０％の多孔質体からなる平均粒径５０μｍ以上、３０ｍｍ以下の粒子であることを特徴としている。但し、粒径１ｍｍに満たない多孔質の粒子を製造することは困難であり、製造面を考慮すると平均粒径１ｍｍ以上とすることが好ましい。なお、ここでいう気孔率とは、水銀圧入法で測定した結果得られる気孔率である。   The second embodiment is characterized in that the halogen gas absorbing material is particles having an average particle diameter of 50 μm or more and 30 mm or less made of a porous body having a porosity of 30% to 70%. However, it is difficult to produce porous particles having a particle diameter of less than 1 mm, and the average particle diameter is preferably 1 mm or more in consideration of the production surface. In addition, the porosity here is a porosity obtained as a result of measuring by the mercury intrusion method.

すなわち、平均粒径を５０μｍ〜３０ｍｍと大きくすることで粒子間の間隔を大きくし、粒子間に流れる被処理ガスの圧損を低減することが可能となり、また、粒径が大きくなることによる、被処理ガスと炭酸ガス吸収材との接触率が低下するのを防止するために、多孔質の粒子を使用するものである。 That is, by increasing the average particle size to 50 μm to 30 mm, it is possible to increase the interval between the particles, to reduce the pressure loss of the gas to be processed flowing between the particles, and to increase the average particle size. In order to prevent the contact rate between the processing gas and the carbon dioxide absorbing material from decreasing, porous particles are used.

すなわち、平均粒径が５０μｍよりも小さくなると、被処理ガスが粒子間を通過するのが困難になり、被処理ガス中のハロゲンガスを効率よく吸収することができなくなり、３０ｍｍよりも大きくなると多孔質体の細孔を通過せずに粒子間を通過する被処理ガス量が多くなり、十分にハロゲンガスを吸収できなくなる恐れがある。   That is, if the average particle size is smaller than 50 μm, it becomes difficult for the gas to be treated to pass between the particles, and the halogen gas in the gas to be treated cannot be efficiently absorbed. There is a possibility that the amount of gas to be processed that passes between the particles without passing through the pores of the material increases, and the halogen gas cannot be sufficiently absorbed.

また、気孔率が３０％よりも少ないとハロゲンガス吸収材と被処理ガスとの接触率が少なくなり、ハロゲンガスの吸収率が低下する恐れがある。気孔率が７０％を超えるとハロゲンガス吸収材自体の量が少なくなり、ハロゲンガス吸収量が少なくなる。また、気孔率が７０％を超えると粒子の強度が低下し、その形状を維持できなくなる恐れがある。   On the other hand, if the porosity is less than 30%, the contact rate between the halogen gas absorbent and the gas to be treated is decreased, and the absorption rate of the halogen gas may be lowered. When the porosity exceeds 70%, the amount of the halogen gas absorbing material itself decreases, and the halogen gas absorption amount decreases. Moreover, when the porosity exceeds 70%, the strength of the particles is lowered, and there is a possibility that the shape cannot be maintained.

また、第２の実施形態におけるハロゲンガス吸収材粒子は柱状体であってもよく、柱状体の場合の粒径は柱状体の長さとする。   In addition, the halogen gas absorbent particles in the second embodiment may be a columnar body, and the particle diameter in the case of the columnar body is the length of the columnar body.

次に、第２の実施形態のハロゲンガス吸収材の製造方法を説明する。   Next, a method for manufacturing the halogen gas absorbent according to the second embodiment will be described.

平均粒径０．１μｍ〜１ｍｍ程度のリチウム複合酸化物粉末を作製する際には、第１の実施形態に述べた転動法を採用すればよい。但し、リチウム複合酸化物粉末とバインダ樹脂粉末との比率を１：０．００１〜０．０５程度に少なくする必要がある。バインダ樹脂の量が０．０５よりも多くなるとバインダ樹脂によって細孔が埋められ、気孔率が３０％以下になる恐れがある。   When producing a lithium composite oxide powder having an average particle size of about 0.1 μm to 1 mm, the rolling method described in the first embodiment may be employed. However, it is necessary to reduce the ratio of the lithium composite oxide powder and the binder resin powder to about 1: 0.001 to 0.05. When the amount of the binder resin is more than 0.05, the pores are filled with the binder resin, and the porosity may be 30% or less.

平均粒径１ｍｍ〜３０ｍｍ程度の炭酸ガス吸収材を作製するには、リチウム複合酸化物粉末を所定サイズの金型などによって圧縮成形すればよい。例えば５００〜１０００ｋｇ／ｍ2程度の圧力をリチウム複合酸化物粉末にかけることで、気孔率３０〜７０％程度の粒子を作製することができる。 In order to produce a carbon dioxide absorbing material having an average particle size of about 1 mm to 30 mm, the lithium composite oxide powder may be compression-molded with a mold having a predetermined size. For example, particles having a porosity of about 30 to 70% can be produced by applying a pressure of about 500 to 1000 kg / m 2 to the lithium composite oxide powder.

図１にハロゲンガス処理装置の一例を示す。   FIG. 1 shows an example of a halogen gas processing apparatus.

処理容器１内には、前述した平均粒径５０μｍ〜３ｍｍのリチウム化複合酸化物粒子からなるハロゲンガス吸収材２が充填されている。また、処理容器１には導入口３と排出口４とが設けられている。   The processing container 1 is filled with the halogen gas absorbent 2 made of the lithiated composite oxide particles having an average particle diameter of 50 μm to 3 mm described above. Further, the processing container 1 is provided with an introduction port 3 and a discharge port 4.

ハロゲンガスを含有する被処理ガス５が導入口３から導入され、充填されたハロゲンガス吸収材２の粒子間を通過する。この時被処理ガス５中のハロゲンガスはハロゲンガス吸収材２によって吸収される。そして、ハロゲンガス吸収材２の粒子間を通過した被処理ガスは、排出口４から排出される。このような処理装置によって、被処理ガス中のハロゲンガス濃度を低減させることができる。   A gas to be treated 5 containing a halogen gas is introduced from the introduction port 3 and passes between the particles of the filled halogen gas absorbent 2. At this time, the halogen gas in the gas to be treated 5 is absorbed by the halogen gas absorber 2. Then, the gas to be processed that has passed between the particles of the halogen gas absorbent 2 is discharged from the discharge port 4. Such a processing apparatus can reduce the halogen gas concentration in the gas to be processed.

実施例１
平均粒径１μｍの金属酸化物（酸化ケイ素）粉末と平均粒径１μｍの炭酸リチウム粉末とを１：２のモル比で混合して混合粉末を得た。この混合粉末を大気中９００℃で焼成して平均粒径１μｍのリチウム化複合酸化物（Li4SiO4）粉末を生成した。 Example 1
A metal oxide (silicon oxide) powder having an average particle diameter of 1 μm and a lithium carbonate powder having an average particle diameter of 1 μm were mixed at a molar ratio of 1: 2 to obtain a mixed powder. This mixed powder was fired at 900 ° C. in the atmosphere to produce a lithiated composite oxide (Li 4 SiO 4 ) powder having an average particle size of 1 μm.

このリチウム化複合酸化物粉末とバインダ樹脂（ＰＶＡ）とを１：０．０１の重量比で混合し、これを転動法により平均粒径５００μｍの顆粒にしてハロゲンガス吸収材を得た。   This lithiated composite oxide powder and binder resin (PVA) were mixed at a weight ratio of 1: 0.01, and this was made into granules having an average particle diameter of 500 μm by a rolling method to obtain a halogen gas absorbent.

次に、以下のようにして得られたハロゲンガス吸収材の特性評価を行った。   Next, the characteristics of the halogen gas absorbent obtained as described below were evaluated.

このハロゲンガス吸収材５０ｇを直径５ｍｍの円筒に充填し、円筒中に被処理ガスを流通させて、ハロゲンガス吸収材と被処理ガスとを接触させた。被処理ガスは窒素ガス９９％、ＨＣｌガス１％の混合ガスで水分を１０００ｐｐｍ含有したものを用い、ガス流量は１ｌ／ｓｅｃで１８０分間流通させた。また、ガス温度は１０℃とした。   The halogen gas absorbing material 50g was filled in a cylinder having a diameter of 5 mm, and the gas to be processed was circulated in the cylinder to bring the halogen gas absorbing material and the gas to be processed into contact with each other. The gas to be treated was a mixed gas of 99% nitrogen gas and 1% HCl gas containing 1000 ppm of water, and the gas flow rate was 1 l / sec for 180 minutes. The gas temperature was 10 ° C.

被処理ガスを通過させた後のハロゲンガス吸収材の構成相をＸ線回折装置で同定したところ酸化ケイ素と塩化リチウムの混合物であることが確認できた。また、ハロゲンガス吸収材の重量を測定したところ、５０ｇの重量増加が認められた。すなわち、ハロゲンガス（塩素ガス）吸収量が５０ｇのであることが分った。   When the constituent phase of the halogen gas absorbent after passing the gas to be treated was identified with an X-ray diffractometer, it was confirmed that it was a mixture of silicon oxide and lithium chloride. Further, when the weight of the halogen gas absorbent was measured, a weight increase of 50 g was observed. That is, it was found that the absorption amount of halogen gas (chlorine gas) was 50 g.

実施例２〜４、参考例１
転動法の条件を変えて、あるいは転動法に代えてスプレードライ法を採用することで、表１に示す平均粒径のハロゲンガス吸収材を作製した。また、作製したハロゲンガス吸収材の組成と、被処理ガスを接触させた前後のハロゲンガス吸収材の重量変化を表１に併記する。 Examples 2-4, Reference Example 1
A halogen gas absorbent having an average particle size shown in Table 1 was produced by changing the conditions of the rolling method or employing a spray drying method instead of the rolling method. Table 1 also shows the composition of the produced halogen gas absorbent and the change in the weight of the halogen gas absorbent before and after contacting the gas to be treated.

実施例５、６
実施例１同様にしてハロゲンガス吸収材を作製し、 被処理ガスとして、ＨＣｌの変りに表１に示すハロゲンガスを使用したことを除き、実施例１と同様にしてハロゲンガス吸収材と被処理ガスとを接触させた。 Examples 5 and 6
A halogen gas absorbing material was produced in the same manner as in Example 1, and the halogen gas absorbing material and the material to be treated were treated in the same manner as in Example 1 except that the halogen gas shown in Table 1 was used instead of HCl as the gas to be treated. Contact with gas.

作製したハロゲンガス吸収材の組成と、被処理ガスを接触させた前後のハロゲンガス吸収材の重量変化を表１に示す。   Table 1 shows the composition of the produced halogen gas absorbent and the change in the weight of the halogen gas absorbent before and after contacting the gas to be treated.

実施例７〜１２
金属酸化物の種類、及び（又は）、金属酸化物と炭酸リチウムとの比率を変えたことを除き、実施例１と同様にしてハロゲンガス吸収材を作製し、さらに実施例１と同様にしてハロゲンガス吸収材と被処理ガスとを接触させた。 Examples 7-12
A halogen gas absorbent was prepared in the same manner as in Example 1 except that the type of metal oxide and / or the ratio between the metal oxide and lithium carbonate was changed. The halogen gas absorber was brought into contact with the gas to be treated.

作製したハロゲンガス吸収材の組成と、被処理ガスを接触させた前後のハロゲンガス吸収材の重量変化を表１に示す。   Table 1 shows the composition of the produced halogen gas absorbent and the change in the weight of the halogen gas absorbent before and after contacting the gas to be treated.

比較例１
リチウム複合酸化物の代わりにソーダライムを使用したことを除き、実施例１と同様にして平均粒径１μｍの炭酸ガス吸収材を作製した。また、この炭酸ガス吸収材を用いて実施例１と同様にして炭酸ガスの吸収量を測定した。その結果を表１に示す。 Comparative Example 1
A carbon dioxide absorbent having an average particle size of 1 μm was prepared in the same manner as in Example 1 except that soda lime was used instead of the lithium composite oxide. Further, the amount of carbon dioxide absorbed was measured in the same manner as in Example 1 using this carbon dioxide absorbent. The results are shown in Table 1.

Figure 0003770608
Figure 0003770608

実施例１３
実施例１と同様にして平均粒径１μｍのリチウム化複合酸化物（Li4SiO4）粉末を生成した。 Example 13
In the same manner as in Example 1, a lithium composite oxide (Li 4 SiO 4 ) powder having an average particle diameter of 1 μm was produced.

このリチウム複合酸化物粉末を金型に入れて圧縮成形して粒径１５ｍｍのハロゲンガス吸収材を得た。この気孔率を測定したところ４０％であった。   This lithium composite oxide powder was put into a mold and compression molded to obtain a halogen gas absorber having a particle size of 15 mm. When this porosity was measured, it was 40%.

このハロゲンガス吸収材の特性評価を実施例１と同様にして行った。その結果を表２に示す。   The characteristics of this halogen gas absorber were evaluated in the same manner as in Example 1. The results are shown in Table 2.

実施例１４〜１７、参考例２〜４
金型を代えたこと、また圧縮力を変化させたことを除き、実施例１３と同様にして、表２に示すサイズ、気孔率のハロゲンガス吸収材を作製した。 Examples 14-17, Reference Examples 2-4
A halogen gas absorbent having the size and porosity shown in Table 2 was produced in the same manner as in Example 13 except that the mold was changed and the compressive force was changed.

また、実施例１と同様にして特性評価を行った。その結果を表２に併記する。   The characteristics were evaluated in the same manner as in Example 1. The results are also shown in Table 2.

実施例１８〜２１
金属酸化物の種類、及び（又は）、金属酸化物と炭酸リチウムとの比率を変えて、表２に示すリチウム化複合酸化物粉末を生成した。 Examples 18-21
The lithiated composite oxide powder shown in Table 2 was produced by changing the kind of metal oxide and / or the ratio of metal oxide and lithium carbonate.

リチウム化複合酸化物の種類を変えたことを除き、実施例１３と同様にしてハロゲンガス吸収材を作製した。   A halogen gas absorber was produced in the same manner as in Example 13 except that the type of lithiated composite oxide was changed.

また、実施例１と同様にして特性評価を行った。その結果を表２に併記する。   The characteristics were evaluated in the same manner as in Example 1. The results are also shown in Table 2.

Figure 0003770608
Figure 0003770608

表１、２から明らかなように実施例のハロゲンガス吸収材は、比較例であるソーダライムと異なり、乾燥したガス中から効率よくハロゲンガスを吸収できることがわかる。   As is clear from Tables 1 and 2, it can be seen that the halogen gas absorbing material of the example can efficiently absorb the halogen gas from the dried gas, unlike the soda lime which is the comparative example.

本発明のハロゲンガス処理装置の実施形態を示す断面図。Sectional drawing which shows embodiment of the halogen gas processing apparatus of this invention.

符号の説明Explanation of symbols

１・・・容器
２・・・炭酸ガス吸収材
３・・・導入口
４・・・排出口
５・・・導入ガス
６・・・排出ガス DESCRIPTION OF SYMBOLS 1 ... Container 2 ... Carbon dioxide gas absorption material 3 ... Inlet 4 ... Discharge port 5 ... Inlet gas 6 ... Exhaust gas

Claims (7)

ハロゲンガスを含有する気体中からハロゲンガスを吸収するハロゲンガス吸収材であって、
平均粒径５０μｍ以上、３ｍｍ以下のリチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有することを特徴とするハロゲンガス吸収材。 A halogen gas absorber that absorbs halogen gas from a gas containing halogen gas,
A halogen gas absorber comprising particles comprising at least one selected from lithium silicate, lithium zirconate, and lithium titanate having an average particle size of 50 μm or more and 3 mm or less. 前記粒子は、Ｌｉ4ＳｉＯ4またはＬｉ2ＺｒＯ3であることを特徴とする請求項１記載のハロゲンガス吸収材。 The halogen gas absorbent according to claim 1, wherein the particles are Li 4 SiO 4 or Li 2 ZrO 3 . ハロゲンガスを含有する気体中からハロゲンガスを吸収するハロゲンガス吸収材であって、
リチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有する気孔率３０％以上、７０％以下の多孔質体からなる平均粒径５０μｍ以上、３０ｍｍ以下の粒子であることを特徴とするハロゲンガス吸収材。 A halogen gas absorber that absorbs halogen gas from a gas containing halogen gas,
It is a particle having an average particle size of 50 μm or more and 30 mm or less composed of a porous material having a porosity of 30% or more and 70% or less containing particles composed of at least one selected from lithium silicate, lithium zirconate, and lithium titanate. Halogen gas absorber. ハロゲンガスを含有する気体を、平均粒径５０μｍ以上、３ｍｍ以下のリチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子に接触させることを特徴とするハロゲンガスの除去方法。   A method for removing a halogen gas, comprising bringing a gas containing a halogen gas into contact with particles composed of at least one selected from lithium silicate, lithium zirconate, and lithium titanate having an average particle size of 50 μm or more and 3 mm or less. ハロゲンガスを含有する気体を、リチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有する気孔率３０％以上、７０％以下の多孔質体からなる平均粒径５０μｍ以上、３０ｍｍ以下の粒子に接触させることを特徴とするハロゲンガスの吸収方法。 A gas containing a halogen gas is an average particle diameter of 50 μm or more and 30 mm made of a porous material having a porosity of 30% or more and 70% or less containing particles composed of at least one selected from lithium silicate, lithium zirconate and lithium titanate. A method for absorbing a halogen gas , comprising contacting the following particles: ハロゲンガスを含有する気体を導入する導入口、及び排出口を有する容器と、
前記容器内に充填された、平均粒径５０μｍ以上、３ｍｍ以下のリチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子とを具備することを特徴とするハロゲンガス処理装置。 A container having an inlet for introducing a gas containing a halogen gas and an outlet;
It filled in the container, an average particle diameter of 50μm or more, 3 mm or less of lithium silicate, lithium zirconate, halogen gas treatment apparatus characterized by comprising a particle element composed of at least one selected from lithium titanate. ハロゲンガスを含有する気体を導入する導入口、及び排出口を有する容器と、
前記容器内に充填された、リチウムシリケート、リチウムジルコネート、リチウムチタネートから選ばれる少なくとも一種からなる粒子を含有する気孔率３０％以上、７０％以下の多孔質体からなる平均粒径５０μｍ以上、３０ｍｍ以下の粒子とを具備することを特徴とするハロゲンガス処理装置。 A container having an inlet for introducing a gas containing a halogen gas and an outlet;
An average particle diameter of 50 μm or more and 30 mm consisting of a porous material having a porosity of 30% or more and 70% or less containing particles composed of at least one selected from lithium silicate, lithium zirconate and lithium titanate filled in the container. A halogen gas processing apparatus comprising the following particles.
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